Use of polyquaternary ammonium methylene phosphonates in chelating or scale inhibition

ABSTRACT

Polyquaternary ammonium methylene phosphonates and uses thereof, particularly as scale inhibitors, chelating agents, bactericides, etc.

This application is a division of Ser. No. 237,883 filed Mar. 24, 1972,now U.S. Pat. No. 3,792,084.

Most commercial water contains alkaline earth metal cations, such ascalcium, barium, magnesium, etc., and anions such as bicarbonate,carbonate, sulfate, oxalate, phosphate, silicate, fluoride, etc. Whencombinations of these anions and cations are present in concentrationswhich exceed the solubility of their reaction products, precipitatesform until their product solubility concentrations are no longerexceeded. For example, when the concentrations of calcium ion andcarbonate ion exceed the solubility of the calcium carbonate reactionproduct, a solid phase of calcium carbonate will form as a precipitate.

Solubility product concentrations are exceeded for various reasons, suchas evaporation of the water phase, change in pH, pressure ortemperature, and the introduction of additional ions which can forminsoluble compounds with the ions already present in the solution.

As these reaction products precipitate on the surfaces of thewater-carrying system, they form scale. The scale prevents effectiveheat transfer, interferes with fluid flow, facilitates corrosiveprocesses, and harbors bacteria. Scale is an expensive problem in manyindustrial water systems, causing delays and shutdowns for cleaning andremoval.

Scale-forming compounds can be prevented from precipitating byinactivating their cations with chelating of sequestering agents, sothat the solubility of their reaction products is not exceeded.Generally, this approach requires many times as much chelating orsequestering agent as cation present, and the use of large amounts oftreating agent is seldom desirable or economical.

It is known that certain inorganic polyphosphates would prevent suchprecipitation when added in amounts far less than the concentrationsneeded for sequestering or chelating. See, for example, Hatch and Rice,"Industrial Engineering Chemistry," Vol. 31, p. 51, at 53; Reitemeierand Buchrer, "Journal of Physical Chemistry," Vol. 44, No. 5, p. 535 at536 (May 1940); Fink and Richardson U.S. Pat. No. 2,358,222; and HatchU.S. Pat. No. 2,539,305. When a precipitation inhibitor is present in apotentially scale-forming system at a markedly lower concentration thanthat required for sequestering the scale forming cation, it is said tobe present in "threshold" amounts. Generally, sequestering takes placeat a weight ratio of threshold active compound to scale-forming cationcomponent of greater than about ten to one, and threshold inhibitiongenerally takes place at a weight ratio of threshold active compound toscale-forming cation component of less than about 0.5 to 1.

The "threshold" concentration range can be demonstrated in the followingmanner. When a typical scale-forming solution containing the cation of arelatively insoluble compound is added to a solution containing theanion of the relatively insoluble compound and a very small amount of athreshold active inhibitor, the relatively insoluble compound will notprecipitate even when its normal equilibrium concentration has beenexceeded. If more of the threshold active compound is added, aconcentration is reached where turbidity or a precipitate of uncertaincomposition results. As still more of the threshold active compound isadded, the solution again becomes clear. This is due to the fact thatthreshold active compounds in high concentrations also act assequestering agents, although sequestering agents are not necessarily"threshold" compounds. Thus, there is an intermediate zone between thehigh concentrations at which threshold active compounds sequester thecations of relatively insoluble compounds and the low concentrations atwhich they act as threshold inhibitors. Therefore, one could also define"threshold" concentrations as all concentrations of threshold activecompounds below that concentration at which this turbid zone orprecipitate is formed. Generally the threshold active compound will beused in a weight ratio of the compound to the cation component of thescale-forming salts which does not exceed about 1.

The polyphosphates are generally effective threshold inhibitors for manyscale-forming compounds at temperatures below 100°F. But after prolongedperiods at higher temperatures, they lose some of their effectiveness.Moreover, in an acid solution, they revert to ineffective or lesseffective compounds.

I have now discovered a process for inhibiting scale such as calcium,barium and magnesium carbonate, sulfate, silicate, etc., scale whichcomprises employing threshold amounts of polyquaternary ammoniummethylene phosphonates.

The term "polyquaternary ammonium methylene phosphonates" includescompositions containing at least two quaternary ammonium groups therein,and having at least one methylene phosphonate group attached to at leastone of the nitrogens of the quaternary ammonium groups, but preferablyhaving at least 4 methylene phosphonate groups in the composition.

The compositions of this invention are polyquaternary ammonium methylenephosphonates. Stated another way, the compositions of this inventionhave a plurality of nitrogen atoms which have been converted to thequaternary state by having

1. nitrogen-bonded methylene phosphonates

2. nitrogen-bonded hydrocarbon groups such as alkyl, alkenyl, aryl,aralkyl, alkaryl, etc.

The quaternary nitrogen are joined together by any suitable bridgingmeans, such as for example a hydrocarbon group such as alkylene,alkenylene, aryl group such as alkaryalkylene such as ##SPC1##

hydrocarbon group containing other than carbon and hydrogen, for examplealkyletheralkylene such as --CH₂ --O--CH₂ CH₂ --, ##EQU1## etc. It isevident that the preferred bridging groups are alkylene terminatedbivalent groups.

Although the polymer may be prepared from unsubstituted mono- orpolyamines, followed by substitution in the nitrogen groups, in order tobetter control the desired products the amines are substituted prior topolymerization. For example, rather than reacting as follows: ##EQU2##and then which is phosphomethylated to yield ##EQU3##

The following reaction can be carried out, where the polyamine in firstphosphomethylated: ##EQU4## to yield the same product.

In addition, the polymeric quaternaries may be formed by reacting:##EQU5##

Stated another way, the amine is first phosphomethylolated to thedesired degree, and this product is then quaternized with a suitablequaternization agent. A monohalide is employed if one does not desire toextend the number of amino groups or by a polyhalide if one desires toextend the number of amino groups.

The amines employed herein are phosphomethylolated preferably by theMannich reaction as illustrated in the following reaction where --NHindicates at least one reactive group on the polyamine: ##EQU6##

The Mannich reaction is quite exothermic and initial cooling willgenerally be required. Once the reaction is well under way, heat may berequired to maintain refluxing conditions. While the reaction willproceed at temperatures over a wide range, i.e., from 80° to 150°C, itis preferred that the temperatures of the reaction medium be maintainedat the refluxing temperatures. The reaction is preferably conducted atatmospheric pressure, although sub-atmospheric and superatmosphericpressures may be utilized if desired. Reaction times will vary,depending upon a number of variables, but the preferred reaction time is1 to 5 hours, and the most preferred reaction time is 21/2 to 31/2hours.

Although the phosphonic acid or the formaldehyde may be added in eitherorder, or together to the reaction mixture, it is preferred to add thephosphonic acid to the amine and then to slowly add the formaldehydeunder refluxing conditions. Generally, about 1/2 to 10 moles or more offormaldehyde and about 1/2 to 10 moles or more of phosphonic acid can beused per mole equivalent of amine, although the most preferred molarequivalent ratios of formaldehyde: phosphonic acid: amine is 1:1:1.Excess formaldehyde and/or phosphonic acid function essentially assolvents, and thus there is no real upper limit on the amount of thesematerials which may be used, per mole equivalent of amine, although suchexcess amounts naturally add to the cost of the final product and aretherefore not preferred. The preferred molar equivalent ratios are 1/2to 2 moles each of the formaldehyde and phosphonic acid per moleequivalent of amine.

The Mannich reaction will proceed in the presence or the absence ofsolvents. The reaction may be carried out as a liquid-phase reaction inthe absence of solvents or diluents, but is preferred that the reactionbe carried out in an aqueous solution containing from about 40 to about50% of the reaction monomers. Preferred conditions for the Mannichreaction include the use of formaldehyde based on the molar equivalentamount of the amine compound, the use of a stoichiometric amount ofphosphonic acid based on the molar equivalent amount of amine (e.g., onthe amine active hydrogen content), refluxing conditions and a pH ofless than 2 and preferably less than 1.

Although formaldehyde is preferred, other aldehydes or ketones may beemployed in place of formaldehyde such as those of the formula ##EQU7##where R and R' are hydrogen, or a hydrocarbon group such as alkyl, i.e.,methyl, ethyl, propyl, butyl, etc., aryl, i.e., phenyl, alkylphenyl,phenalkyl, etc., cycloalkyl, i.e., cyclohexyl, etc.

The compound can also be prepared by a modified Mannich reaction byemploying a chloromethylene phosphonate. ##EQU8##

X--Z--X may be a wide variety of polymerizing compounds, i.e., capableof joining amino groups, where Z may be alkylene, alkenylene,alkynylene, alkaralkylene, an alkyleneether-containing group, anester-containing group, an amido-containing group, etc., and X is ahalide.

The following are non-limiting examples:

I. Saturated dihalides

    X--Z--X

where Z is alkylene, straight chain or branched, for example X(CH₂)_(n)X where n is 2-25 or more, for example 2-10, but preferably 2-4. The(CH₂)_(n) may be branched such as where at least one of the H's is ahydrocarbon group such as alkyl, i.e., methyl, ethyl, etc., substitutedsuch as halo, hydroxy, etc.

II. Aralkylene dihalides

    X--Z--X

where Z is aralkylene having for example 8-30 or more carbons, such as8-20 carbons, but preferably xylylene.

The following are illustrative examples: ##SPC2##

Additional examples of aralkylene radicals include those of the formula--CH₂ --Ar--CH₂ -- where AR is ##SPC3##

III. Alkylene Ethers

    X--A--X

where A is an alkyleneether radical --A(OA)_(n) -- where A is alkylene(including cycloalkylene ether radicals) having for example from 1--10or more carbons such as 1--4, but preferably 2 in each alkylene unit.Typical examples are

    Cl--CH.sub.2 CH.sub.2 --O--CH.sub.2 CH.sub.2 --Cl

    Cl--CH.sub.2 CH.sub.2 (O CH.sub.2 CH.sub.2).sub.1-10.sup.-Cl ##EQU9##

    Cl--CH.sub.2 CH.sub.2 O--CH.sub.2 O--CH.sub.2 CH.sub.2 --Cl

Additional examples of A include groups of the formula (AO)_(n) where Ais ##EQU10## where Y is alkyl, for example ##EQU11##

Thus, A can be methylene, polymethylene, ethylene, propylene, butylene,octylene, etc. In addition (AO)_(n) may be homo or hetero as to A, toyield for example (ETO)_(a) (PrO)_(b), (PrO)_(a) (BuO)_(b), or(PrO-ETO)_(n) ;

    --CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 --

etc.

These compounds also include the formal of ethylene chlorohydrin andbromohydrin, for example ClCH₂ CH₂ OCH₂ OCH₂ CH₂ Cl, ClCH₂ CH₂ OCH₂ CH₂OCH₂ OCH₂ CH₂ OCH₂ CH₂ Cl etc.

IV. Unsaturated dihalides

    X--Z--X

where Z is an unsaturated aliphatic radical, for example

    --CH.sub.2 --CH = CH--CH.sub.2 --

    --ch.sub.2 --c .tbd. c--ch.sub.2 --, etc.

Among the polyamines employed herein are polyalkylenepolyamines, forexample, of the formula ##EQU12## where n is an interger, for example 1to 25 or more, such as 2 to 10, but preferably 2 to 5, etc., and A is analkylene group --(CH₂)_(m) -- where m is 2 to 10 or more, but preferablyethylene or propylene.

One or more of the hydrogens on the CH₂ group may be substituted, forexample, by such groups as alkyl groups, for example, methyl, ethyl,etc. Examples of A include ##EQU13##

Examples of polyamines include the following: diethylene triamine,dipropylene triamine, triethylene tetramine, tripropylene tetramine,tetraethylene pentamine, tetrapropylene pentamine, polyalkyleneimines,i.e., the higher molecular weight amines derived from alkyleneimine suchas polyethyleneimines, polypropyleneimines, for example, having 50, 100or more alkylene amino units, etc. Mixtures of the above polyamineamines and those polyamines containing both ethylene and propylenegroups, for example: ##EQU14##

These include the following: ##EQU15##

In addition, the starting polyamine may be of a technical grade such as"Amine E-100" from Dow Chemical Company. Amine E-100 is the stillbottoms from a polyalkylene polyamine process with the followingapproximate composition:

                               Percent                                            H                                                                             Tetraethylene pentamine (H.sub.2 N(CH.sub.2 CH.sub.2 N).sub.4 H)                                         10                                                 H                                                                             Pentaethylene hexamine (H.sub.2 N(CH.sub.2 CH.sub.2 N).sub.5 H)                                          40                                                 Cyclics (piperazines)      20                                                 Branched structure         20                                                 Polymers (chains with more than five ethylene                                                            10                                                      amine groups)                                                             Other suitable amines are the polyethyleneimine series from Dow Chemical     Company.

Also included within the terms polyalkylene polyamine are substitutedpolyamines such as N-alkyl, N-aryl, etc., compositions ##EQU16##provided some groups are present capable of forming methylenephosphonates.

Illustrative examples are ##EQU17## where R is alkyl, aryl, alkenyl,etc., such as hexyl, dodecyl, etc.

Also included are acylated polyalkylenepolyamines such as alkyl, aryl,alkenyl, etc., for example, where ##EQU18## is a acetyl, benzoic, etc.

The following equation illustrates the reaction of epichlorohydrin withpolyethylenepolyamines, ideally presented: ##EQU19##

The above is an idealized presentation, but the invention does notexclude other related reactions such as certain amounts of crosslinking,etc.

The reaction with dichlorodiethyl ether may be ideally presented asfollows where the R's are ##EQU20## groups: ##EQU21## with alkylenedichlorides the reaction is ##EQU22## with butene dichloride thereaction is ##EQU23## with butyne dichloride the reaction is ##EQU24##with aralylarylene the reaction is ##EQU25##

Polyquaternaries can also be prepared from methylene phosphonates ofammonia or monoamines, for example ##EQU26## where XZX has the meaningstated above, or according to the equation ##EQU27## where R is asubstituted group such as alkyl, aryl, alkenyl, alkaryl, aralkyl,cycloalkyl, etc.

The following are representative examples.

                  TABLE I                                                         ______________________________________                                        Ex.       Formula                                                             ______________________________________                                                 O                                                                             ∥                                                                    CH.sub.2 P(OH).sub.2                                                          |                                                           1.       ------.sup.+N------(CH.sub.2).sub.4 --                                        Br.sup.-|                                                            CH.sub.2 P(OH).sub.2                                                          ∥                                                                    O                                                                             .sub.n                                                                        CH.sub.3                                                                      |                                                           2.       ------.sup.+N------(CH.sub.2).sub.4 --                                        Br.sup.-|                                                            CH.sub.2 P(OH).sub.2                                                          ∥                                                                    O                                                                             .sub.n                                                                        C.sub.2 H.sub.5                                                               |                                                           3.       ------.sup.+N------CH.sub.2 --CH=CH--CH.sub.2 --                              Cl.sup.-|                                                            CH.sub.2 P(OH).sub.2                                                          ∥                                                                    O                                                                             .sub.n                                                                        CH.sub.2                                                                      |                                                           4.       ------.sup.+N------CH.sub.2 CH.sub.2 --                                       Cl.sup.-|                                                            CH.sub.2 P(OH).sub.2                                                          ∥                                                                    O                                                                             .sub.n                                                                        CH.sub.3                                                                      |                                                           5.       ------.sup.+N------CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --                    Cl.sup.-|                                                            CH.sub.2 P(OH).sub.2                                                          ∥                                                                    O                                                                             .sub.n                                                               6.       ------.sup.+N------(CH.sub.2).sub.4 --                                        Br.sup.-|                                                            CH.sub.2 P(OH).sub.2                                                          ∥                                                                    O                                                                             .sub.n                                                                        CH.sub.3                                                                      |                                                           7.       ------.sup.+N--CH.sub.2 CH.sub.2 --                                           Cl.sup.-|                                                            CH.sub.2 P(OH).sub.2                                                          ∥                                                                    O                                                                             .sub.n                                                                        O                                                                             ∥                                                                    CH.sub.2 P(OH).sub.2                                                          |                                                           8.       ------.sup.+N------CH.sub.2 --CH=CH--CH.sub.2 --                              Cl.sup.- |O                                                          |∥                                                          CH.sub.2 P(OH).sub.2                                                          .sub.n                                                                        CH.sub.2 C.sub.12 H.sub.25                                                    |                                                           9.       ------.sup.+N------(CH.sub.2).sub.4 --                                        Br.sup.-|O                                                           |∥                                                          CH.sub.2 P(OH).sub.2                                                          .sub.n                                                                        O                                                                             ∥                                                                    CH.sub.2 P(OH).sub.2                                                          |                                                           10.      ------.sup.+N----(CH.sub.2).sub.4 --                                          Br.sup.-|                                                            C.sub.12 H.sub.25                                                             .sub.n                                                               ______________________________________                                    

The methylene phosphonate group may be in the free acid or salt form.The salt moiety can vary widely to include any suitable metal, ammonia,organic ammonium form of an amine, etc., cation such as an alkali metal,i.e., sodium, potassium, etc., a monoamine such as methyl amine, ethylamine, etc., polyamines such as ethylene diamine, propylene diamine, thecorresponding polyamines such as diethylene triamine, triethylenetetramines, etc.; alkanolamines such as ethanolamine, diethanolamine,propanolamines, etc.; cyclic-amines such as piperidine, morpholine, etc.Thus, any salt moiety capable of carrying out this invention can beemployed.

Thus, the term "methylene phosphonate" includes ##EQU28## groups as wellas substituted methylene groups, i.e., ##EQU29## where R is the groupderived from the aldehyde or ketone reacted, for example, those statedherein. The phosphonate can exist as the free acid or as the salt##EQU30## where M is hydrogen or a salt moiety.

USE AS SCALE INHIBITOR

Scale formation from aqueous solutions containing an oxide variety ofscale forming compounds, such as calcium, barium and magnesiumcarbonate, sulfate, silicate, oxalates, phosphates, hydroxides,fluorides and the like are inhibited by the use of threshold amounts ofthe compositions of this invention which are effective in small amounts,such as less than 100 ppm, and are preferably used in concentrations ofless than 25 ppm.

The compounds of the present invention (e.g., the acid form of thecompounds) may be readily converted into the corresponding alkali metal,ammonium or alkaline earth metal salts by replacing at least half of thehydrogen ions in the phosphonic acid group with the appropriate ions,such as the potassium ion or ammonium or with alkaline earth metal ionswhich may be converted into the corresponding sodium salt by theaddition of sodium hydroxide. If the pH of the amine compound isadjusted to 7.0 by the addition of caustic soda, about one half of the--OH radicals on the phosphorous atoms will be converted into the sodiumsalt form.

The scale inhibitors of the present invention illustrate improvedinhibiting effect at high temperatures when compared to prior artcompounds. The compounds of the present invention will inhibit thedeposition of scale-forming alkaline earth metal compounds on a surfacein contact with aqueous solution of the alkaline earth metal compoundsover a wide temperature range. Generally, the temperatures of theaqueous solution will be at least 40°F., although significantly lowertemperatures will often be encountered. The preferred temperature rangefor inhibition of scale deposition is from about 130° to about 350°F.The aqueous solutions or brines requiring treatment generally containabout 50 ppm to about 50,000 ppm of scale-forming salts. The compoundsof the present invention effectively inhibit scale formation whenpresent in an amount of from 0.1 to about 100 ppm, and preferably 0.2 to25 ppm wherein the amounts of the inhibitor are based upon the totalaqueous system. There does not appear to be a concentration below whichthe compounds of the present invention are totally ineffective. A verysmall amount of the scale inhibitor is effective to a correspondinglylimited degree, and the threshold effect is obtained with less than 0.1ppm. There is no reason to believe that this is the minimum effectiveconcentration. The scale inhibitors of the present invention areeffective in both brine, such as sea water, and acid solutions.

In the specific examples the general method of phosphomethylolation isthat disclosed in Netherlands Pat. Nos. 6407908 and 6505237 and in theJournal of Organic Chemistry, Vol. 31, No. 5, 1603-1607 (May, 1966).These references are hereby incorporated by reference.

CALCIUM SCALE INHIBITION TEST

The procedure utilized to determine the effectiveness of the scaleinhibitors in regard to calcium scale is as follows:

Several 50 ml. samples of a 0.04 sodium bicarbonate solution are placedin 100 ml. bottles. To these solutions is added the inhibitor in variousknown concentrations. 50 ml. samples of a 0.02 M CaCl₂ solution are thenadded.

A total hardness determination is then made on the 50-50 mixtureutilizing the well known Schwarzenbach titration. The samples are placedin a water bath and heated at 180°F. 10 ml. samples are taken from eachbottle at 2 and 4 hour periods. These samples are filtered throughmillipore filters and the total hardness of the filtrates are determinedby titration. ##EQU31##

The tables describe the scale inhibition test results obtained forspecific compositions.

The following examples illustrate the reaction of a phosphomethylatedpolyamine with a chain extender, i.e., dihalide

GROUP A EXAMPLE A1

Into a suitable reaction vessel were charged 41 g. of (H₂ PO₃ CH₂)₂ NCH₂CH₂ N(CH₂ PO₃ H₂)₂ and 50 ml. of water. To the resulting solution wasadded 12.5 g of 1,4-dichlorobutene-2. This mixture was stirred andheated at reflux temperatures until homogeneous (24 hours). The productwas a viscous liquid that was quite soluble in additional water.

EXAMPLE A2

Into a suitable reaction vessel were charged 41 g. of (H₂ PO₃ CH₂)₂ NCH₂CH₂ N(CH₂ PO₃ H₂)₂ and 50 ml. of water. To the resulting solution wasadded 21.6 g. of 1,4-dibromobutane. The resulting mixture was stirredand heated at reflux temperatures for 24 hours. The product solution wasquite viscous and water soluble.

EXAMPLE A3

Into a suitable reaction vessel were charged 42.5 g. of (H₂ PO₃ CH₂)₂NCH₂ CH₂ CH₂ N(CH₂ PO₃ H₂)₂ and 50 ml. of water. To the resultingsolution was added 12.5 g. of 1,4-dichlorobutene-2. The resultingmixture was stirred and heated at reflux temperatures for 24 hours. Theresulting product solution was viscous and soluble in additional water.

Since the examples described herein are similarly prepared, they will bepresented in Table II to save repetitive details.

                  TABLE II                                                        ______________________________________                                        CH.sub.2 PO.sub.3 H.sub.2 CH.sub.2 PO.sub.3 H.sub.2                           ||                                                          --N.sup.+--------R----N.sup.+--------R'----                                   ||                                                          CH.sub.2 PO.sub.3 H.sub.2 CH.sub.2 PO.sub.3 H.sub.2                           X.sup.- X.sup.+                                                               Example R        R'                  X                                        ______________________________________                                        A4      (CH.sub.2).sub.4                                                                       (CH.sub.2).sub.4    Br                                       A5      (CH.sub.2).sub.4                                                                       CH.sub.2 --CH=CH--CH.sub.2                                                                        Cl                                       A6      (CH.sub.2).sub.4                                                                       (CH.sub.2).sub.5    Br                                       A7      (CH.sub.2).sub.3                                                                       (CH.sub.2).sub.4    Br                                       A8      (CH.sub.2).sub.2             Cl                                       A9      (CH.sub.2).sub.2                                                                       (CH.sub.2).sub.5    Br                                        A10    (CH.sub.2).sub.6                                                                       (CH.sub.2).sub.4    Br                                       ______________________________________                                    

                  TABLE A                                                         ______________________________________                                        Inhibition of scale formation from a CaCO.sub.3 solution at 180°F.     for                                                                           four hours (200 ppm CaCO.sub.3)                                                                               %                                             Inhibitor     Salt   Conc. (ppm)                                                                              Scale Inhibitor                               ______________________________________                                        Example A1    H      20         59                                            Example A1    H      50         64                                            Example A2    H      20         57                                            Example A2    H      50         66                                            Example A3    H      20         52                                            Example A3    H      50         61                                            Example A4    H      20         61                                            Example A4    H      50         68                                            Example A4    Na     20         59                                            Example A4    Na     50         65                                            Commercial organic                                                                          Na     20         35                                            phosphate inhibitor                                                                         Na     50         40                                            Commercial organic                                                                          Na     20         35                                            phosphonate inhibitor                                                                       Na     50         42                                            ______________________________________                                    

The following examples illustrate the reaction of a phosphomethylatedpolyamines with a non-chain extender, i.e., a monohalide.

GROUP B EXAMPLE B1

Into a small pressure reaction vessel were charged 44.0 g. of tetrakis(dihydrogen phosphonomethyl) ethylene diamine and 44 ml. of water. Tothis stirred solution was added 11.0 g. of methyl chloride. Theresulting mixture was stirred and heated at 80°C. for 24 hours. Theproduct solution gave a positive test with "Indiquat Test Paper"indicating the presence of quaternary ammonium salts. The product wasindicated to be: ##EQU32##

EXAMPLE B2

Into a small pressure reaction vessel were charged 57.8 g. of pentakis(dihydrogen phosphonomethyl) diethylene triamine and 58 ml. of water. Tothis stirred solution was added 33.0 g. of ethyl bromide. The resultingmixture was stirred and heated at 80°C. for 24 hours. The productsolution was completely soluble in water. The product was indicated tobe: ##EQU33## A portion of the product was neutralized with 50% NaOH.

EXAMPLE B3

Into a suitable pressure reaction vessel was introduced 144 g. of a 50%aqueous solution of hexakis (dihydrogen phosphonomethyl)triethylene-tetramine. To this solution was added 21 g. of methylchloride. This mixture was stirred and heated at 80°C. for 24 hours. Theproduct was indicated to be: ##EQU34## A portion of this product wasconverted into the ammonium salt with aqueous ammonium hyroxide.

EXAMPLE B4

Into a suitable pressure reaction vessel was introduced 172 g. of a 50%aqueous solution of heptakis (dihydrogen phosphonomethyl) tetraethylenepentamine. To this solution was added 71 g. of methyl iodide. Theresulting mixture was stirred and heated at 80°C. for 8 hours. Theresulting solution was homogeneous and dissolved easily in water. Theproduct was indicated to be: ##EQU35## A portion of the product wasneutralized with aqueous KOH.

EXAMPLE B5

Into a suitable pressure reaction vessel were introduced 53 g. oftetrakis (dihydrogen phosphonomethyl) diethylene triamine N-hydroxyethyland 53 ml. of water. To this solution was added 15.5 g. of methylchloride. The mixture was stirred and heated at 80°C. for 24 hours. Theproduct was indicated to be: ##EQU36## Since the examples describedherein are similarly prepared, they will be presented in Table III tosave repetitive details.

                  TABLE III                                                       ______________________________________                                        Example B6                                                                    Cl.sup.-Cl.sup.-                                                              (H.sub.2 PO.sub.3 CH.sub.2).sub.2 N.sup.+CH.sub.2 CH.sub.2 N.sup.+(CH.sub.    2 PO.sub.3 H.sub.2).sub.2                                                     Example B7                                                                    Br.sup.-C.sub.4 H.sub.9 Br.sup.-Br.sup.-                                      |                                                                    (H.sub.2 PO.sub.3 CH.sub.2).sub.2 N.sup.+CH.sub.2 CH.sub.2 N.sup.+CH.sub.2     CH.sub.2 N.sup.+(CH.sub.2 PO.sub.3 H.sub.2).sub.2                            |||                                                C.sub.4 H.sub.9 C.sub.4 H.sub.9 C.sub.4 H.sub.9                               Example B8                                                                    C.sub.2 H.sub.5 I.sup.-C.sub.2 H.sub.5 I.sup.-                                ||                                                          (H.sub.2 PO.sub.3 CH.sub.2)N.sup.+CH.sub.2 CH.sub.2 N.sup.+(CH.sub.2          PO.sub.3 H.sub.2).sub.2                                                       |                                                                    C.sub.3 H.sub.7 OH                                                            Example B9                                                                    Br.sup.-Br.sup.-                                                              (H.sub.2 PO.sub.3 CH.sub.2).sub.2 N.sup.+CH.sub.2 CH.sub.2 N.sup.+(CH.sub.    2 PO.sub.3 H.sub.2).sub.2                                                     ||                                                          C.sub.12 H.sub. 25 C.sub.12 H.sub.25                                          Example B10                                                                   CH.sub.3 CH.sub.3                                                             ||                                                          CH.sub.2 PO(OH).sub.2 N.sub.+C.sub.2 H.sub.4 N.sub.+CH.sub.2 PO(OH).sub.2     H.sub.2 PO(OH).sub.2                                                          25                                                                            Cl.sup.-Cl.sup.-                                                              ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        Inhibition of Scale Formation from a CaCO.sub.3 solution at                   180°F. for four hours (200 ppm CaCO.sub.3).                            Inhibitor  Salt   Conc. (ppm)                                                                              % Scale Inhibition                               ______________________________________                                        Example B1 H      50         54                                               Example B1 H      20         50                                               Example B2 H      50         67                                               Example B2 H      20         57                                               Example B2  Na    50         60                                               Example B2  Na    20         53                                               Example B3 H      50         52                                               Example B3 H      20         45                                               Example B3  Na    50         50                                               Example B3  Na    20         40                                               Example B4 H      50         64                                               Example B4 H      20         50                                               Example B5 H      50         60                                               Example B5 H      20         45                                               Example B5  Na    50         55                                               Example B5  Na    20         48                                               Commercial Or-                                                                ganic phosphate                                                               inhibitor   Na    50         40                                                  "        Na    20         35                                               Commercial Or-                                                                ganic phosphon-                                                               ate inhibitor                                                                             Na    50         42                                                  "        Na    20         35                                               ______________________________________                                    

The following examples illustrate the reaction of phosphomethylolatedmonoamines with difunctional dihalides.

GROUP C EXAMPLE C1

Into a suitable reaction vessel were charged 26.4 g. of C₄ H₉ N(CH₂ PO₃H₂)₂ and 26.4 of water. This mixture was neutralized with 50% NaOH. Tothe resulting solution was added 6.3 g. of 1,4-dichlorobutene-2. Thismixture was heated to reflux and held there until homogeneous (5 hours).The product was: ##EQU37##

EXAMPLE C2

Into a suitable reaction vessel were charged 14.5 g. of C₆ H₁₁ N(CH₂ PO₃H₂)₂ and 14.5 g. of water. This mixture was neutralized with 50% NaOH.To the resulting solution was added 5.4 g. of 1,4-dibromobutane. Thismixture was heated to reflux and held there until homogeneous (6 hours).The solution gave a positive test with "Indiquat Test Paper" indicatingthe presence of quaternary nitrogen groups.

The product was: ##EQU38##

EXAMPLE C3

Into a suitable reaction vessel were charged 20 g. of C₁₂ H₂₅ N(CH₂ PO₃H₂)₂, 20 g. of water and 10 g. of isopropanol. This mixture wasneutralized with 50% NaOH. To the resulting solution was added 5.4 g. of1,4-dibromobutane. This mixture was heated to reflux and held there for5 hours. The product solution dissolved easily in water and foamedstrongly. The product was: ##EQU39##

Since the examples described herein are similarly prepared, they will bepresented in Table IV to save repetitive details.

                  TABLE IV                                                        ______________________________________                                        X.sup.-X.sup.-                                                                (H.sub.2 PO.sub.3 CH.sub.2).sub.2 N.sup.+N.sup.+(CH.sub.2 PO.sub.3            H.sub.2).sub.2                                                                ||                                                          RR                                                                            Example R                          X                                          ______________________________________                                        C4     C.sub.2 H.sub.5                                                                          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                               Cl                                     C5     C.sub.3 H.sub.7                                                                          CH.sub.2 CH.sub.2    Br                                     C6     CH.sub.3                        Cl                                     C7                CH.sub.2 CH.sub.2    Br                                     C8     C.sub.2 H.sub.5 OH                                                                       CH.sub.2 CH=CHCH.sub.2                                                                             Cl                                     C9     C.sub.2 H.sub.5                                                                          CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                                Br                                     C10    C.sub.12 H.sub.25                                                                        CH.sub.2 CH.sub.2    Br                                     C11    C.sub.14 H.sub.29                                                                        CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                                Br                                     C12    C.sub.18 H.sub.37                                                                        CH.sub.2 CH.sub.2    Br                                     RX.sup.-RX.sup.-                                                              ||                                                          (H.sub.2 PO.sub.3 CH.sub.2)N.sup.+N.sup.+(CH.sub.2 PO.sub.3 H.sub.2)          ||                                                          RR                                                                            C13    C.sub.2 H.sub.5                                                                          CH.sub. 2 CH.sub.2 CH.sub.2 CH.sub.2                                                               Br                                     C14               CH.sub.2 CH.sub.2    Br                                     C15    C.sub.2 H.sub.5 OH                                                                       CH.sub.2 CH=CHCH.sub.2                                                                             Cl                                     C16               CH.sub.2 CH.sub.2    Br                                     C17               CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                              Br                                     C18    C.sub.3 H.sub.9                 Br                                     ______________________________________                                    

                  TABLE C                                                         ______________________________________                                        Inhibition of Scale Formation from a CaCO.sub.3 solution at                   180°F. for four hours (200 ppm CaCO.sub.3).                            Inhibitor  Salt   Conc. (ppm)                                                                              % Scale Inhibition                               ______________________________________                                        Example C1 Na     50         64                                               Example C1 Na     20         54                                               Example C2 Na     50         68                                               Example C2 Na     20         59                                               Example C2 H      50         70                                               Example C2 H      20         59                                               Example C4 Na     50         65                                               Example C4 Na     20         55                                               Example C13                                                                              Na     50         48                                               Example C13                                                                              Na     20         40                                               Example C15                                                                              Na     50         65                                               Example C15                                                                              Na     20         59                                               ______________________________________                                    

USE IN THE CHELATION OR SEQUESTRATION OF METAL IONS

The chelating or sequestering agents of the present invention are ofwide utility such as when it becomes necessary to sequester or inhibitthe precipitation of metal cations from aqueous solutions. Among theirmany uses are the following applications:

Soaps and detergents, textile processing, metal cleaning and scaleremoval, metal finishing and plating, rubber and plastics, industry,pulp and paper industry, oil-well treatment, chelation in biologicalsystems.

An important function of these compounds is their ability to sequesterFe.sup.⁺². In secondary oil recovery by means of water floods, watersare frequently mixed on the surface prior to injection. Frequently thesewaters contain amounts of Fe.sup.⁺² and H₂ S. If these incompatiblewaters are mixed, an FeS precipitate results which can plug the sandface of the injection well. Another of their functions is to preventformation of gelatinous iron hydroxides in the well and in the effluentproduction waters.

To demonstrate the effectiveness of the polyquaternary ammoniummethylene phosphonates in chelating Fe.sup.⁺², the following testprocedure was utilized. Into a flask that contained a knownconcentration of the sequestering agent, and enough sodium hydroxide orhydrochloric acid to give the desired pH was placed a 100 ml. aqueoussample of ferrous ammonium sulfate (20 ppm of (Fe.sup.⁺²); after finalpH adjustment the solution was allowed to remain at ambient temperaturesfor 48 hours. The solution was centrifuged for one hour to removecollodial iron hydroxide and an aliquot of the supernatant solution wasanalyzed by atomic absorption to determine the iron concentration.

The following table illustrates the ability of the sequestering agentsof the present invention to sequester Fe.sup.⁺², as compared to the wellknown sequestering agent tetrasodium ethylenediamine tetra-acetate(EDTA).

                  TABLE V                                                         ______________________________________                                                  Sequestering   Amount of iron                                       pH        Agent (ppm)    Sequestered (ppm)                                    ______________________________________                                        5         A1      (50)       (12)                                             5         A2      (50)       ( 9)                                             5         B1      (50)       ( 7)                                             5         C1      (50)       (14)                                             5         EDTA    (50)       ( 7)                                             7         A1      (50)       (12)                                             7         A2      (50)       ( 9)                                             7         B1      (50)       ( 7)                                             7         C1      (50)       (13)                                             7         EDTA    (50)       ( 7)                                             10        A1      (150)      ( 9)                                             10        A2      (150)      ( 7)                                             10        B1      (150)      ( 6)                                             10        C1      (150)      (10)                                             10        EDTA    (150)      ( 6)                                             ______________________________________                                    

As one can observe from the preceding table, the sequestering agents ofthis invention are as effective, and in some cases superior, to EDTAwhen tested over a wide pH range.

The sequestering agents of this invention are also quite effective insequestering other metal cations in aqueous solutions. For example, atest was conducted in which 60 ppm of the sequesterant were dissolved in100 ml. of water. The pH was adjusted to 9 and maintained there. Metalcations were added, in the following amounts, before a noticeableprecipitate was formed.

                  TABLE VI                                                        ______________________________________                                        Sequesterant Metal (ppm) Sequestered per                                                   60 ppm of Sequesterant                                           ______________________________________                                        Product                                                                       Example A1   Fe.sup.+.sup.3                                                                              ( 70)                                              Example A1   A1.sup..sup.+3                                                                              (120)                                              Example A1   Cu.sup..sup.+2                                                                              (120)                                              Example A1   Ni.sup..sup.+2                                                                              ( 60)                                              Example B1   Fe.sup..sup.+3                                                                              ( 60)                                              Example B1   A1.sup..sup.+3                                                                              ( 70)                                              Example B1   Cu.sup..sup.+2                                                                              ( 70)                                              Example B1   Ni.sup..sup.+3                                                                              ( 50)                                              ______________________________________                                    

Other heavy metals sequestered by the sequestering agents of thisinvention such as cobalt, manganese, chromium and the like.

The amount employed to chelate is controlled by stoichiometry incontrast to scale inhibition where the amount employed is threshold orless than stoichiometric.

USE AS A MICROBIOCIDE I. IN WATER TREATMENT

This phase of the present invention relates to the treatment of water.More particularly, it is directed to providing improved means forcontrolling microbiological organisms including bacteria, fungi, algae,protozoa, and the like, present in water.

It is well known that ordinary water contains various bacteria, fungi,algae, protozoa and other microbiological organisms which, ifuncontrolled, multiply under certain conditions so as to present manyserious problems. For example, in swimming pools the growth of thesemicrobiological organisms is very undesirable from a sanitary standpointas well as for general appearances and maintenance. In industrial watersystems such as cooling towers, condenser boxes, spray condensers, watertanks, basins, gravel water filters, and the like, microbiologicalorganisms may interfere greatly with proper functioning of equipment andresult in poor heat transfer, clogging of systems and rotting of woodenequipment, as well as many other costly and deleterious effects.

In other industrial applications where water is used in processes, asfor example, as a carrying medium, etc., microbiological organisms mayalso constitute a problem in maintenance and operation. Illustrative ofsuch industrial applications are the pulp and paper manufacturingprocesses, oil well flooding operations and the like.

The products of this invention are suitable as biocides for industrial,agricultural and horticultural, military, hygienic and recreationalwater supplies. They provide an inexpensive, easily prepared group ofproducts which can be used, in minimal amounts, in water supplies, incooling towers, air-conditioning systems, on the farm and ranch, in thefactory, in civilian and military hospitals and dispensaries, in camps,for swimming pools, baths and aquaria, waterworks, wells, reservoirs, byfire-fighting agencies, on maritime and naval vessels, in boilers,steam-generators and locomotives, in pulp and paper mills, forirrigation and drainage, for sewage and waste disposal, in the textileindustry, in the chemical industries, in the tanning industry, etcetera, and which will render said water supplies bactericidal,fungicidal and algicidal. They further provide a simple process wherebywater supplies, for whatever purposes intended, are renderedbacteriostatic, fungistatic and algistatic, i.e., said water suppliestreated by the process of this invention will resist and inhibit thefurther growth or proliferation of bacteria, fungi, algae and all formsof microbial life therein.

II. WATER FLOODING IN SECONDARY RECOVERY OF OIL

This phase of the present invention relates to secondary recovery of oilby water flooding operations and is more particularly concerned with animproved process for treating flood water and oil recovery therewith.More particularly this invention relates to a process of inhibitingbacterial growth in the recovery of oil from oil-bearing strata by meansof water flooding taking place in the presence of sulfatereducingbacteria.

Water flooding is widely used in the petroleum industry to effectsecondary recovery of oil. By employing this process the yield of oilfrom a given field may be increased beyond the 20 - 30 percent of theoil in a producing formation that is usually recovered in the primaryprocess. In flooding operations, water is forced under pressure throughinjection wells into or under oil-bearing formations to displace the oiltherefrom to adjacent producing wells. The oil-water mixture is usuallypumped from the producing wells into a receiving tank where the water,separated from the oil, is siphoned off, and the oil then transferred tostorage tanks. It is desirable in carrying out this process to maintaina high rate of water injection with a minimum expenditure of energy. Anyimpediment to the free entry of water into oil bearing formationsseriously reduces the efficiency of the recovery operation.

The term "flood water" as herein employed is any water injected into oilbearing formations for the secondary recovery of oil. In conventionaloperations, the water employed varies from relatively pure spring waterto brine and is inclusive of water reclaimed from secondary recoveryoperations and processed for recycling. The problems arising from thewater employed depend in part on the water used. However, particularlytroublesome and common to all types of water are problems directly orindirectly concerned with the presence of microorganisms, such asbacteria, fungi and algae. Microorganisms may impede the free entry ofwater into oil-bearing formations by producing ions susceptible offorming precipitates, forming slime and/or existing in sufficiently highnumbers to constitute an appreciable mass, thereby plugging the pores ofthe oil-bearing formation. Pore-plugging increases the pressurenecessary to drive a given volume of water into an oil-bearing formationand oftentimes causes the flooding water to by-pass the formation to beflooded. In addition, microorganisms may bring about corrosion by actingon the metal structures of the wells involved, producing corrosivesubstances such as hydrogen sulfide, or producing conditions favorableto destructive corrosion such as decreasing the pH or producing oxygen.The products formed as the result of corrosive action may also bepore-plugging precipitates. Usually, the difficulties encountered are acombination of effects resulting from the activity of differentmicroorganisms.

III. HYDROCARBON TREATMENT

This phase of the present invention relates to the use of thesecompounds as biocides in hydrocarbon systems.

In addition to being used as biocides in aqueous systems, the compoundsof this invention can also be employed as biocides in hydrocarbonsystems, particularly when petroleum products are stored. It is believedthat bacteria and other organisms, which are introduced into hydrocarbonsystems by water, feed readily on hydrocarbons resulting in a loss inproduct; that microorganisms cause the formation of gums, H₂ S,peroxides, acids and slimes at the interface between water and oil; thatbacterial action is often more pronounced with rolling motion than understatic conditions, etc. Loss of product, corrosion of the storage tank,clogging of filters and metering instruments, and fuel deterioration areamong the harmful effects of bacteria growth in fuels. The activity ofmicroorganism growth is often increased by the presence of rust. Notonly do these microorganisms often encourage rust but rust encouragesmicroorganism growth. Since microorganism growth appears to beconsiderably higher with kerosene than with gasoline, plugged filtersexperienced with jet fuels which contain large amounts of kerosene is aserious problem.

The compositions of this invention can be employed in hydrocarbonsystems.

MICROBIOCIDAL TESTING:

The screening procedure was as follows: a one percent by weight solutionof the test compound in water was prepared. The solution was asepticallyadded to a sterile broth that would support the growth of the testorganism, Desulfovibro desulfuricans, to provide a concentration of 50and 100 parts by weight of test compound per million parts by weight ofbroth. A general growth medium, such as prescribed by the AmericanPetroleum Institute was used. The broth containing the test compoundthen was dispersed in 5 cc. amounts into sterile disposable tubes andthe tubes were inoculated with the growing test organism and incubatedat 35°C. for 24 hours. The absence of presence of growth of themicroorganisms was determined by visual inspection by an experiencedobserver.

Following is a summary of the results of the testing of examples of thisinvention.

    ______________________________________                                        Compound     Concentration of                                                 Example No.  Test Compound  Results                                           ______________________________________                                        C3           25 ppm         *Gave control                                     C10          25 ppm          Gave control                                     C11          40 ppm          Gave control                                     ______________________________________                                         *by control is meant that the test compound was biostatic or biocidal -       i.e., no growth of the test organism occurred under the test conditions. 

I claim:
 1. The process of chelating or inhibiting the formation ofscale in an aqueous system which comprises treating said system with apolyquaternary ammonium methylene, or substituted methylene, phosphonatewherein all the methylene, or substituted methylene, phosphonate groupsare nitrogen-bonded, wherein the substituted methylene moieties eachconsist of methylene substituted by at least one hydrocarbon group,wherein there are up to two such methylene, or substituted methylene,phosphonate groups bonded to a quaternary ammonium nitrogen atom andhaving at least one methylene, or substituted methylene, phosphonategroup attached to at least one of such nitrogens, there being at leasttwo quaternary ammonium groups in the polyquaternary ammonium moiety ofthe phosphonate.
 2. The process of claim 1 where, each quaternarynitrogen of the polyquaternary phosphonates, contains at least 2methylene, or substituted methylene, phosphonate groups.
 3. The processof claim 1 where the polyquaternaries have repeating units of thegeneral formula ##EQU40## where R is ##EQU41## or a hydrocarbon group,and A is a bridging group, M is hydrogen, ammonium, organic ammonium, oran alkali metal or an alkaline earth metal, and X is halogen, thebridging group A being an alkylene terminated bivalent hydrocarbon grouphaving 8 to 30 carbons, or alkylene-ether containing group of theformula A'-(OA')_(n) where A' is alkylene having 1 to 10 carbons and nis 1 to 10, or an alkylene group having 2 to 25 carbons unsubstituted orsubstituted by OH or halogen.
 4. The process of claim 1 where thepolyquaternaries are of the general formula ##EQU42## where R is ahydrocarbon or OH substituted hydrocarbon group, A is a bridging group,and X is a halogen, and M is a hydrogen, ammonium, organic ammonium, oran alkali metal or alkaline earth metal, the bridging group A being analkylene terminated bivalent hydrocarbon group.
 5. The process of claim1 where the polyquaternaries are of the general formula ##EQU43## whereR is a hydrocarbon group or OH substituted hydrocarbon group, A is abridging group, and X is a halogen and M is a hydrogen, ammonium,organic ammonium, or an alkali metal or alkaline earth metal, thebridging group A being a bivalent alkylene terminated hydrocarbon group.6. The process of claim 4 where the hydrocarbon moiety of R is saturatedcontaining up to 18 carbon atoms or is phenyl and where the bridginggroup A contains from 2 to 30 carbon atoms and is aliphatic or isaralkylene.
 7. The process of claim 5 where the hydrocarbon moiety of Ris saturated containing up to 18 carbon atoms or is phenyl and where thebridging group A contains from 2 to 30 carbon atoms and is aliphatic oris aralkylene.
 8. The process of claim 4 where the polyquaternary is##EQU44## or its sodium salt.
 9. The process of claim 5 where thepolyquaternary is ##EQU45## or its sodium salt.
 10. The process of claim5 where the polyquaternary is ##EQU46## or its sodium salt, and where##SPC4##designates C₆ H₁₁.